CN101255113B - Methylacrylic acid polyethylene glycol single armor ether ester and preparation method thereof - Google Patents
Methylacrylic acid polyethylene glycol single armor ether ester and preparation method thereof Download PDFInfo
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- CN101255113B CN101255113B CN2007101684855A CN200710168485A CN101255113B CN 101255113 B CN101255113 B CN 101255113B CN 2007101684855 A CN2007101684855 A CN 2007101684855A CN 200710168485 A CN200710168485 A CN 200710168485A CN 101255113 B CN101255113 B CN 101255113B
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Abstract
The invention relates to a preparation method of poly(ethyleneglycol monomethylether) methacrylate, wherein the reactants components (percentage by weight) comprises: 9. 32 by weight of methacrylic acid, 39. 4 by weight of poly(ethylene glycol) methyl ether, 3-7 by weight of reaction activating agent, 0. 01-0. 2 by weight of side reaction suppressing agent, and 40-60 by weight of water-carrying agent; adding all the components into a reactor by the proportion, slowly heating up, preserving heat at 80 degree C for 0. 5-1h, slowly raising temperature until the reactants azeotropy, reacting for 6-8h, naturally cooling to room temperature, and removing the impurity to obtain ethyleneglycol monomethylether methacrylate. The synthetic poly(ethyleneglycol monomethylether) methacrylate by the method has steady quality, the esterification ratio can reach over 99%, the poly(ethyleneglycol monomethylether) methacrylate can be directly used for synthesizing polycarboxylic type concrete water-reducer and other surface active agents, the prepared concrete water-reducer therewith has a high water-reducing ratio, and reaching to more than 28 (wherein the mix amount is 0. 25) which has a better performance than like products, can satisfy the require for development of high performance concrete, and has a wide application prospect.
Description
Technical field
The invention belongs to the preparation method of Methylacrylic acid polyethylene glycol single armor ether ester.
Technical background
China is that cement output and usage quantity occupy the first in the world, and according to authoritative expectation, China's cement output will reach 1,000,000,000 tons in 2005.Along with China's rapid economy development, country can rise to concrete demand and performance requriements year by year to the increasing of Infrastructure and dwelling construction dynamics, and concrete high-performanceization is an inexorable trend.Equally, also can constantly increase demand with the little high efficiency water reducing agent of high water reducing rate and slump-loss.At present, the high efficiency water reducing agent annual requirement of China reaches 1,000,000 tons.Naphthalene water reducer is the main product of the present high efficiency water reducing agent of China, 80% of the market share of standing, but naphthalene series high-efficiency water-reducing agent is because water-reducing rate is not high, concrete slump loss is too fast, be difficult to satisfy the requirement of modern high performance Concrete Construction, and composite prod quality instability often has influence on concrete setting and harden and weather resistance.Using formaldehyde in synthetic has certain pollution to environment, impels the research and development to other new and effective water reducer.Polycarboxylic acid series high efficiency water reducing agent has high water reducing ability, high workability, low slump loss, excellent comprehensive performances such as drying shrinkage is little.Poly carboxylic acid series water reducer reaches super dispersed by electrostatic repulsion forces and space steric effect dual function, and its unique dispersion mechanism is that new road has been opened up in the research of new dispersant with high efficiency.From the design and the modification of molecular structure, the type and the collocation of easier adjustment molecular weight, functional group synthesize new and effective water reducer rational in infrastructure, excellent performance.At present, the development of external polycarboxylic acid series high efficiency water reducing agent has obtained remarkable progress, and many industrialization are arranged, and has obtained abroad using widely, has been substituted s-generation naphthalene water reducer.There are Gray's Si building materials company (GRACECONSTRUCTION PRODUCTS) of the U.S., the special building material technique company (MASTER BUILDERTECHNOLOY) of Mace, Italian Ma Bei company (MAPEI), Switzerland Sequa Corp (SIKA), Japanese Kao company (KAO CORP) etc. in the multinational enterprise that has now entered into China high efficiency water reducing agent market, and they are capturing suitable share on market.(as Three Gorges Dam Project, Shanghai Jin Mao Tower, Shanghai magnetic suspension train, Construction of Hangzhou Bay Cross-sea Bridge etc.) used poly carboxylic acid series water reducer dependence on import almost completely in some heavy constructions of China.Therefore research and develop polycarboxylic acid series high efficiency water reducing agent, adapt to the needs of new engineering, no matter in theory, still very important meaning is arranged all in practical application, become one of high efficiency water reducing agent research and development most active fields.
The preparation of Methylacrylic acid polyethylene glycol single armor ether ester is one of gordian technique of synthesizing polycarboxylic acid dehydragent.Introduce side chain polyoxyethylene thiazolinyl chain by big monomer in the water reducer molecular structure, sterically hindered effect is provided, the dispersion dispersed and good for the contribution of water reducer molecule keeps performance.The basic assurance of the over-all properties that therefore synthetic high-quality big monomer is a water reducer.At present synthetic big monomer methods has methacrylic acid direct esterification method, methyl methacrylate ester-interchange method, maleic anhydride esterification method, directly refines method, enol and ethylene oxide polymerization method.Wherein adopt the raw material of methacrylic acid direct esterification method to purchase easily, easy control of reaction conditions, less demanding to equipment all can meet the needs of production with regard to general existing chemical plant facility simultaneously; Non-environmental-pollution.The big monomer mass of present method synthetic is stable, and esterification yield can reach more than 99%, and the water reducer of preparation has high water reducing rate, surpasses the like product performance.
Summary of the invention:
The preparation method of Methylacrylic acid polyethylene glycol single armor ether ester is characterized in that reactant, component (weight percent) are:
All reactants are put into the reaction vessel that has water-and-oil separator by above reactant composition, slowly heating (1～2 ℃/min), at 80 ℃ of insulation 0.5～1h, slow again elevated temperature (1～2 ℃/min), until the reactant azeotropic, reaction 6～8h naturally cools to room temperature, remove impurity, obtain Methylacrylic acid polyethylene glycol single armor ether ester.Wherein: reacting movable agent is composited by 1: 1: 1 (weight ratio) by tosic acid, sodium pyrosulfate and gac; Side reaction inhibitor is composited by 1: 1: 1 (weight ratio) by Resorcinol, MEHQ and iron trichloride; The dispersion train aqua is composited by 4: 1 (weight ratio) by toluene and hexanaphthene.
Specific embodiment:
Table 1 specific embodiment
Wherein: reacting movable agent is composited by 1: 1: 1 (weight ratio) by tosic acid, sodium pyrosulfate and gac;
Side reaction inhibitor is composited by 1: 1: 1 (weight ratio) by Resorcinol, MEHQ and iron trichloride;
The dispersion train aqua is composited by 4: 1 (weight ratio) by toluene and hexanaphthene.
Table 2 performance evaluation
Claims (1)
1. the preparation method of Methylacrylic acid polyethylene glycol single armor ether ester is characterized in that reactant composition (weight percent) is:
Methacrylic acid: 8.65～9.32%
Poly glycol monomethyl ether: 39.4%
Reacting movable agent: 3～7%
Side reaction inhibitor: 0.01～0.2%
Dispersion train aqua: 40～60%
By above component all reactants are put into the reaction vessel that has water-and-oil separator, slowly heating is at 80 ℃ of insulation 0.5～1h, slow again elevated temperature, until the reactant azeotropic, reaction 6～8h, naturally cool to room temperature, remove impurity, obtain Methylacrylic acid polyethylene glycol single armor ether ester;
Described reacting movable agent is composited by 1: 1: 1 (weight ratio) by tosic acid, sodium pyrosulfate and gac;
Described side reaction inhibitor is composited by 1: 1: 1 (weight ratio) by Resorcinol, MEHQ and iron trichloride;
Described dispersion train aqua is composited by 4: 1 (weight ratio) by toluene and hexanaphthene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101684855A CN101255113B (en) | 2007-11-28 | 2007-11-28 | Methylacrylic acid polyethylene glycol single armor ether ester and preparation method thereof |
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| CN2007101684855A CN101255113B (en) | 2007-11-28 | 2007-11-28 | Methylacrylic acid polyethylene glycol single armor ether ester and preparation method thereof |
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| CN101255113A CN101255113A (en) | 2008-09-03 |
| CN101255113B true CN101255113B (en) | 2011-07-20 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101704934B (en) * | 2009-11-20 | 2012-05-30 | 山东同盛建材有限公司 | Method for synthesizing polycarboxylate superplasticizer at low cost |
| CN102093553B (en) * | 2010-12-02 | 2012-08-29 | 中国海洋石油总公司 | Method for synthesizing polycarboxylate series water-reducing agent macromonomer |
| CN106145741A (en) * | 2015-04-09 | 2016-11-23 | 张耀忠 | A kind of polycarboxylic acid water reducer macromer and preparation method thereof |
| CN105439852B (en) * | 2015-12-04 | 2017-12-05 | 湖北航天化学技术研究所 | A kind of synthetic method of the single-ended ether-ether series compound of polyalkylene glycol acrylate |
| CN114106269A (en) * | 2021-12-20 | 2022-03-01 | 江苏尼高科技有限公司 | High-performance viscosity-reduction type polycarboxylate concrete water reducer and preparation method thereof |
| CN114395091A (en) * | 2021-12-31 | 2022-04-26 | 南京瑞固聚合物有限公司 | Mud-resistant polycarboxylic acid water reducing agent and synthesis process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1636922A (en) * | 2004-12-10 | 2005-07-13 | 武汉理工大学 | Concrete water reducing agent of polycarboxylic acid and its prepn process |
| CN1724447A (en) * | 2005-06-09 | 2006-01-25 | 武汉理工大学 | Water reducing agent of poly carboxylic acid series concrete and its preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1636922A (en) * | 2004-12-10 | 2005-07-13 | 武汉理工大学 | Concrete water reducing agent of polycarboxylic acid and its prepn process |
| CN1724447A (en) * | 2005-06-09 | 2006-01-25 | 武汉理工大学 | Water reducing agent of poly carboxylic acid series concrete and its preparation process |
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